New Internal Alkynes Catalysed by a Cobalt(II) Coordination Polymer … · 2019. 8. 1. ·...

S1

Supporting Information:

Highly Efficient and Selective Hydroboration of Terminal and Internal Alkynes Catalysed by a Cobalt(II) Coordination Polymer

Guoqi Zhang,*,a Sihan Li,a,b Jing Wu,a,b Haisu Zeng,a,b Zixuan Mo,a Keziah Davisa and Shengping Zhengb

a Department of Sciences, John Jay College and Ph.D. Program in Chemistry, The Graduate Center of the City University of New York, New York, 10019 NY, USA. Email: [email protected] Department of Chemistry, Hunter College, the City University of New York, New York, 10065 NY, USA.

Electronic Supplementary Material (ESI) for Organic Chemistry Frontiers.This journal is © the Partner Organisations 2019

S2

Experimental DetailsGeneral Considerations. Unless specified otherwise, all reactions were carried out under a dry N2 atmosphere using standard glove-box and Schlenk techniques. Anhydrous grade solvents and reagents used were obtained from Aldrich or Fisher Scientific and stored over 4 Å molecular sieves. All chemicals of analytical grade including the alkene substrates and additives are used as received from Aldrich, Alfa Aesar, Acros or Fisher Scientific without further purification. 1H NMR and 13C NMR spectra were obtained at room temperature on a Bruker AV 500 or 600 MHz NMR spectrometer, with chemical shifts (δ) referenced to the residual solvent signal. GC-MS analysis was obtained using a Shimadzu GCMS-QP2010S gas chromatograph mass spectrometer (column: SHRX1-5MS, thickness: 0.25 m, diameter: 0.25 mm, length: 30.0 m; conditions: 30-200 °C, 10 °C/min, injection temperature: 100 °C; solvent cutoff: 3 min). Co(tpy)Cl2 and 1 were prepared according to literature procedures.1

General Procedure for 1-Catalyzed Alkyne Hydroboration. In a glovebox under N2 atmosphere, cobalt catalyst 1 (0.11 mg, 0.25 μmol, 0.025 mol%) and KOtBu (0.56 mg, 1 mol%) was dissolved in THF (1.0 mL) in a 5 mL glass vial equipped with a stir bar. The mixture was stirred for 1 min. Alkynes (1.0 mmol) and pinacolborane (141 mg, 1.1 mmol) were then added. The reaction mixture was allowed to stir at room temperature for indicated time periods (10-30 min) and then the reaction was quenched by exposing the reaction solution to air and adding CH2Cl2 (2 mL) to the solution. The crude reaction mixture was first analyzed by GC-MS (dilute solution in CH2Cl2) to determine the yield and selectivity of desired alkenylboronates. The reaction mixture was then evaporated under reduced pressure and the product was purified through a SiO2 column chromatography using ethyl acetate/hexane as an eluent. The pure alkenylboronate products were characterized by 1H and 13C NMR spectroscopies.

Mercury-poisoning Experiment for Hydroboration of Phenylacetylene. In a glovebox under N2 atmosphere, cobalt catalyst 1 (0.11 mg, 0.25 μmol, 0.025 mol%) and KOtBu (0.56 mg, 1 mol%) was dissolved in THF (1.0 mL) in a 5 mL glass vial equipped with a stir bar. The mixture was stirred for 1 min and then Hg (~0.5 g) was added. Alkynes (1.0 mmol) and pinacolborane (141 mg, 1.1 mmol) were then added. The reaction mixture was allowed to stir at room temperature for 10 min and then the reaction was quenched by exposing the reaction solution to air and adding CH2Cl2 (2 mL) to the solution. The crude reaction mixture was analyzed by GC-MS using hexamethylbenzene as an internal standard and 84% yield of 2a was observed.

Chemoselective Hydroboration of Alkyne vs. Alkene. In a glovebox under N2 atmosphere, cobalt catalyst 1 (0.11 mg, 0.25 μmol, 0.025 mol%) and KOtBu (0.56 mg, 1 mol%) was dissolved in THF (1.0 mL) in a 5 mL glass vial equipped with a stir bar. The mixture was stirred for 1 min. Styrene (104 mg, 1.0 mmol), phenylacetylene (102 mg, 1.0 mmol) and pinacolborane (128 mg, 1.0 mmol) were then added. The reaction mixture was allowed to stir at room temperature for 10 min and then the reaction was quenched by exposing the reaction solution to air and adding CH2Cl2 (2 mL) to the solution. The crude reaction mixture was analyzed by GC-MS using hexamethylbenzene as an internal standard. The results show 88% conversion of phenylacetylene and >95% recycle of styrene.

S3

Deuterium-Labeling Experiment. In a glovebox under N2 atmosphere, cobalt catalyst 1 (0.11 mg, 0.25 μmol, 0.025 mol%) and KOtBu (0.56 mg, 1 mol%) was dissolved in THF (1.0 mL) in a 5 mL glass vial equipped with a stir bar. The mixture was stirred for 1 min. Phenylacetylene-D1 (103 mg, 1.0 mmol) and pinacolborane (141 mg, 1.1 mmol, 1.1 eq.) were then added. The reaction mixture was allowed to stir at room temperature for additional 10 min. The reaction was exposed to the air and quenched with aq. NaHCO3, and then extracted with Et2O. The product was isolated (201 mg, 86%) by column chromatography (silica gel) using ethyl acetate/hexane (1:20, v/v) as an eluent. The product was characterized by 1H, 2H and 13C NMR spectroscopies.

+ BO

OH

1 (0.1 mol%)KOtBu (1 mol%)

THF, rt, 10 min

H BPin

DD

4

Catalytic reactions and characterization details

2a2: In a glovebox under N2 atmosphere, cobalt catalyst 1 (0.11 mg, 0.25 μmol, 0.025 mol%) and KOtBu (0.56 mg, 1 mol%) was dissolved in THF (1.0 mL) in a 3.8 mL glass vial equipped with a stir bar. The mixture was stirred for 1 min. Phenylacetylene (102 mg, 1.0 mmol) and pinacolborane (141 mg, 1.1 mmol) were then added. The reaction mixture was allowed to stir at room temperature for 10 min. The reaction was quenched by exposing the reaction solution to air and

adding CH2Cl2 (2 mL) to the solution. The crude reaction mixture was analyzed by GC-MS and then purified through a column chromatography (silica gel) using ethyl acetate/hexane (1:20, v/v) as an eluent. Colorless oil of 2a was isolated. Yield: 189 mg (82%). 1H NMR (600 MHz, CDCl3) δ 7.49 (d, J = 7.2 Hz, 2H), 7.40 (d, J = 18.4 Hz, 1H), 7.34 (t, J = 7.5 Hz, 2H), 7.30 (d, J = 7.3 Hz, 1H), 6.17 (d, J = 18.4 Hz, 1H), 1.32 (s, 12H) ppm; 13C NMR (150 MHz, CDCl3) δ 149.8, 137. 8, 129.3, 128.9, 127.4, 83.7, 25.2 ppm. GC-MS (m/z): 230 (calc. 230).

2b3: In a glovebox under N2 atmosphere, cobalt catalyst 1 (0.11 mg, 0.25 μmol, 0.025 mol%) and KOtBu (0.56 mg, 1 mol%) was dissolved in THF (1.0 mL) in a 3.8 mL glass vial equipped with a stir bar. The mixture was stirred for 1 min. 4-tert-Butylphenylacetylene (158 mg, 1.0 mmol) and pinacolborane (141 mg, 1.1 mmol) were then added. The reaction mixture was allowed to stir at room temperature for 10 min. The reaction was quenched by exposing the reaction solution to air and adding CH2Cl2 (2 mL) to the solution. The crude reaction mixture was analyzed by GC-MS and then purified through a

column chromatography (silica gel) using ethyl acetate/hexane (1:20, v/v) as an eluent. Colorless oil of 3c was isolated. Yield: 172 mg (60%). 1H NMR (500 MHz, CDCl3) δ 7.47 (d, J = 8.5 Hz, 2H), 7.44 (s, 1H), 7.40 (d, J = 8.4 Hz, 2H), 6.17 (d, J = 18.4 Hz, 1H), 1.35 (s, 24H, overlapping) ppm; 13C NMR (126 MHz, CDCl3) δ 152.4, 149.7, 135.0, 127.1, 125.8, 83.6, 35.0, 31.6, 25.1 ppm. GC-MS (m/z): 286 (calc. 286).

Chemical Formula: C14H19BO2Molecular Weight: 230.1140

B O

O


B O

O

S4

2c2: In a glovebox under N2 atmosphere, cobalt catalyst 1 (0.11 mg, 0.25 μmol, 0.025 mol%) and KOtBu (0.56 mg, 1 mol%) was dissolved in THF (1.0 mL) in a 3.8 mL glass vial equipped with a stir bar. The mixture was stirred for 1 min. 4-Fluorophenylacetylene (120 mg, 1.0 mmol) and pinacolborane (141 mg, 1.1 mmol) were then added. The reaction mixture was allowed to stir at room temperature for 10 min. The reaction was quenched by exposing the reaction solution to air and adding CH2Cl2 (2 mL) to the solution. The crude

reaction mixture was analyzed by GC-MS and then purified through a column chromatography (silica gel) using ethyl acetate/hexane (1:20, v/v) as an eluent. Yellowish oil of 2c was isolated. Yield: 154 mg (62%). 1H NMR (500 MHz, CDCl3) δ 7.51 – 7.42 (m, 2H), 7.35 (d, J = 18.5 Hz, 1H), 7.07 – 6.98 (m, 2H), 6.07 (d, J = 18.4 Hz, 1H), 1.31 (s, 12H) ppm; 13C NMR (150 MHz, CDCl3) δ 164.1, 161.9, 148.2, 128.7 (d, J = 8.2 Hz), 115.6 (d, J = 21.7 Hz), 83.4, 24.8 ppm. GC-MS (m/z): 248 (calc. 248).

2d3: In a glovebox under N2 atmosphere, cobalt catalyst 1 (0.11 mg, 0.25 μmol, 0.025 mol%) and KOtBu (0.56 mg, 1 mol%) was dissolved in THF (1.0 mL) in a 3.8 mL glass vial equipped with a stir bar. The mixture was stirred for 1 min. 2-Fluorophenylacetylene (120 mg, 1.0 mmol) and pinacolborane (141 mg, 1.1 mmol) were then added. The reaction mixture was allowed to stir at room temperature for 20 min. The reaction was quenched by exposing the

reaction solution to air and adding CH2Cl2 (2 mL) to the solution. The crude reaction mixture was analyzed by GC-MS and then purified through a column chromatography (silica gel) using ethyl acetate/hexane (1:20, v/v) as an eluent. Yellowish oil of 2d was isolated. Yield: 184 mg (74%). 1H NMR (500 MHz, CDCl3) δ 7.65 – 7.52 (m, 2H, overlapping), 7.26 (s, 1H), 7.15 – 7.09 (m, 1H, overlapping), 7.07 – 6.99 (m, 1H), 6.24 (d, J = 18.7 Hz, 1H), 1.31 (s, 12H) ppm; 13C NMR (126 MHz, CDCl3) δ 161.8, 159.8, 141.4 (d, J = 4.0 Hz), 130.3 (d, J = 8.5 Hz), 127.5 (d, J = 3.3 Hz), 125.4 (d, J = 11.6 Hz), 124.2 (d, J = 3.6 Hz), 115.9 (d, J = 22.1 Hz), 83.5, 24.9 ppm. GC-MS (m/z): 248 (calc. 248).

2e2: In a glovebox under N2 atmosphere, cobalt catalyst 1 (0.11 mg, 0.25 μmol, 0.025 mol%) and KOtBu (0.56 mg, 1 mol%) was dissolved in THF (1.0 mL) in a 3.8 mL glass vial equipped with a stir bar. The mixture was stirred for 1 min. 4-Bromophenylacetylene (180 mg, 1.0 mmol) and pinacolborane (141 mg, 1.1 mmol) were then added. The reaction mixture was allowed to stir at room temperature for 10 min. The reaction was quenched by exposing the reaction solution to air and adding CH2Cl2 (2 mL) to the solution.

The crude reaction mixture was analyzed by GC-MS and then purified through a column chromatography (silica gel) using ethyl acetate/hexane (1:20, v/v) as an eluent. Yellowish oil of 2d was isolated. Yield: 185 mg (60%). 1H NMR (500 MHz, CDCl3) δ 7.45 (d, J = 6.6 Hz, 2H), 7.34 (d, J = 8.4 Hz, 2H), 7.28 (d, J = 18.5 Hz, 1H), 6.15 (dd, J = 18.4, 2.5 Hz, 1H), 1.31 (s, 12H) ppm; 13C NMR (150 MHz, CDCl3) δ 148.1, 136.4, 133.6, 131.8, 131.7, 128.6, 123.0, 83.6, 24.9 ppm. GC-MS (m/z): 309 (calc. 309).1H NMR (500 MHz, Chloroform-d)

Chemical Formula: C14H18BFO2Molecular Weight: 248.1044

B O

O

F

Chemical Formula: C14H18BBrO2Molecular Weight: 309.0100

B O

O

Br

Chemical Formula: C14H18BFO2Molecular Weight: 248.1044

B O

O

F

S5

2f2: In a glovebox under N2 atmosphere, cobalt catalyst 1 (0.11 mg, 0.25 μmol, 0.025 mol%) and KOtBu (0.56 mg, 1 mol%) was dissolved in THF (1.0 mL) in a 3.8 mL glass vial equipped with a stir bar. The mixture was stirred for 1 min. 4-Methoxyphenylacetylene (132 mg, 1.0 mmol) and pinacolborane (141 mg, 1.1 mmol) were then added. The reaction mixture was allowed to stir at room temperature for 30 min. The reaction was quenched by exposing the reaction solution to air and adding CH2Cl2 (2 mL) to the solution. The crude

reaction mixture was analyzed by GC-MS and then purified through a column chromatography (silica gel) using ethyl acetate/hexane (1:20, v/v) as an eluent. Yellowish oil of 2d was isolated. Yield: 161 mg (62%). 1H NMR (500 MHz, CDCl3) δ 7.43 (d, J = 8.3 Hz, 2H), 7.36 (d, J = 18.5 Hz, 1H), 6.85 (d, J = 8.3 Hz, 2H), 6.02 (d, J = 17.7 Hz, 1H), 3.78 (s, 3H), 1.30 (s, 12H) ppm; 13C NMR (126 MHz, CDCl3) δ 160.3, 149.1, 133.6, 128.5, 114.0, 113.9, 83.2, 55.2, 24.8 ppm. GC-MS (m/z): 260 (calc. 260).

2g4: In a glovebox under N2 atmosphere, cobalt catalyst 1 (0.11 mg, 0.25 μmol, 0.025 mol%) and KOtBu (0.56 mg, 1 mol%) was dissolved in THF (1.0 mL) in a 3.8 mL glass vial equipped with a stir bar. The mixture was stirred for 1 min. 3,5-Dimethoxyphenylacetylene (162 mg, 1.0 mmol) and pinacolborane (141 mg, 1.1 mmol) were then added. The reaction mixture was allowed to stir at room temperature for 10 min. The reaction was quenched by exposing the reaction solution to air and adding CH2Cl2 (2 mL) to the solution. The crude reaction mixture was analyzed by GC-

MS and then purified through a column chromatography (silica gel) using ethyl acetate/hexane (1:20, v/v) as an eluent. Yellowish oil of 2g was isolated. Yield: 189 mg (65%). 1H NMR (500 MHz, CDCl3) δ 7.31 (d, J = 18.3 Hz, 1H), 6.65 (s, 2H), 6.41 (s, 1H), 6.13 (d, J = 18.4 Hz, 1H), 3.77 (s, 6H), 1.30 (s, 12H) ppm; 13C NMR (126 MHz, CDCl3) δ 160.8, 149.4, 139.5, 105.0, 101.3, 83.4, 55.3, 24.8 ppm. GC-MS (m/z): 290 (calc. 290). 1H NMR (500 MHz, Chloroform-d)

2h2: In a glovebox under N2 atmosphere, cobalt catalyst 1 (0.11 mg, 0.25 μmol, 0.025 mol%) and KOtBu (0.56 mg, 1 mol%) was dissolved in THF (1.0 mL) in a 3.8 mL glass vial equipped with a stir bar. The mixture was stirred for 1 min. Ethynylcyclohexane (108 mg, 1.0 mmol) and pinacolborane (141 mg, 1.1 mmol) were then added. The reaction mixture was allowed to stir at room temperature for 5 min. The reaction was quenched by exposing the reaction solution to air and adding CH2Cl2 (2 mL) to the solution. The crude reaction mixture

was analyzed by GC-MS and then purified through a column chromatography (silica gel) using ethyl acetate/hexane (1:20, v/v) as an eluent. Colorless oil of 2h was isolated. Yield: 213 mg (90%). 1H NMR (500 MHz, CDCl3) δ 6.55 (dd, J = 18.2, 6.1 Hz, 1H), 5.35 (d, J = 18.2 Hz, 1H), 2.08 – 1.91 (m, 1H), 1.74 – 1.66 (m, 4H), 1.64 – 1.59 (m, 1H), 1.24 (d, J = 2.2 Hz, 14H, overlapping), 1.14 – 1.02 (m, 3H) ppm; 13C NMR (126 MHz, CDCl3) δ 159.9, 115.2, 83.0, 43.3, 31.9, 26.2, 26.0, 24.8 ppm. GC-MS (m/z): 236 (calc. 236).


B O

O

O


B O

O


B O

OO

O

S6

2i2: In a glovebox under N2 atmosphere, cobalt catalyst 1 (0.11 mg, 0.25 μmol, 0.025 mol%) and KOtBu (0.56 mg, 1 mol%) was dissolved in THF (1.0 mL) in a 3.8 mL glass vial equipped with a stir bar. The mixture was stirred for 1 min. 1-Hexyne (82 mg, 1.0 mmol) and pinacolborane (141 mg, 1.1 mmol) were then added. The reaction mixture was allowed to stir at room temperature for 5 min. The

reaction was quenched by exposing the reaction solution to air and adding CH2Cl2 (2 mL) to the solution. The crude reaction mixture was analyzed by GC-MS and then purified through a column chromatography (silica gel) using ethyl acetate/hexane (1:20, v/v) as an eluent. Colorless oil of 2i was isolated. Yield: 172 mg (82%). 1H NMR (500 MHz, CDCl3) δ 6.63 (dt, J = 17.9, 6.4 Hz, 1H), 5.42 (dd, J = 18.0, 1.6 Hz, 1H), 2.18 – 2.11 (m, 2H), 1.39 (q, J = 7.3 Hz, 2H), 1.35 – 1.30 (m, 2H), 1.26 (s, 12H), 0.91 – 0.85 (m, 3H) ppm; 13C NMR (126 MHz, CDCl3) δ 155.2, 83.3, 35.9, 30.7, 25.1, 22.6, 14.3 ppm. GC-MS (m/z): 210 (calc. 210).

2j2: In a glovebox under N2 atmosphere, cobalt catalyst 1 (0.11 mg, 0.25 μmol, 0.025 mol%) and KOtBu (0.56 mg, 1 mol%) was dissolved in THF (1.0 mL) in a 3.8 mL glass vial equipped with a stir bar. The mixture was stirred for 1 min. 3,3-Dimethyl-1-butyne (82 mg, 1.0 mmol) and pinacolborane (141 mg, 1.1 mmol) were then added. The reaction mixture was allowed to stir at room temperature for 5 min. The reaction was quenched by exposing the reaction solution to air

and adding CH2Cl2 (2 mL) to the solution. The crude reaction mixture was analyzed by GC-MS and then purified through a column chromatography (silica gel) using ethyl acetate/hexane (1:20, v/v) as an eluent. Colorless oil of 2j was isolated. Yield: 168 mg (80%). 1H NMR (500 MHz, CDCl3) δ 6.63 (d, J = 17.6 Hz, 1H), 5.34 (d, J = 18.5 Hz, 1H), 1.26 (s, 12H), 1.01 (s, 9H) ppm; 13C NMR (126 MHz, CDCl3) δ 164.5, 83.1, 35.1, 28.9, 24.9 ppm. GC-MS (m/z): 210 (calc. 210).

2k3: In a glovebox under N2 atmosphere, cobalt catalyst 1 (0.11 mg, 0.25 μmol, 0.025 mol%) and KOtBu (0.56 mg, 1 mol%) was dissolved in THF (1.0 mL) in a 3.8 mL glass vial equipped with a stir bar. The mixture was stirred for 1 min. Trimethylsilylacetylene (98 mg, 1.0 mmol) and pinacolborane (141 mg, 1.1 mmol) were then added. The reaction mixture was allowed to stir at room temperature for 5 min. The reaction was quenched by exposing the reaction

solution to air and adding CH2Cl2 (2 mL) to the solution. The crude reaction mixture was analyzed by GC-MS and then purified through a column chromatography (silica gel) using ethyl acetate/hexane (1:20, v/v) as an eluent. Colorless oil of 2k was isolated. Yield: 192 mg (85%). 1H NMR (5600 MHz, CDCl3) δ 7.12 (d, J = 21.8 Hz, 1H), 6.24 (d, J = 21.8 Hz, 1H), 1.28 (s, 12H), 0.07 (s, 9H) ppm; 13C NMR (126 MHz, CDCl3) δ 158.1, 83.5, 24.9, -1.71 ppm. GC-MS (m/z): 226 (calc. 226).

2l3: In a glovebox under N2 atmosphere, cobalt catalyst 1 (0.11 mg, 0.25 μmol, 0.025 mol%) and KOtBu (0.56 mg, 1 mol%) was dissolved in THF (1.0 mL) in a 3.8 mL glass vial equipped with a stir bar. The mixture was stirred for 1 min. Ethynylcyclopropane (132 mg, 1.0 mmol) and pinacolborane (141 mg, 1.1 mmol) were then added. The


B O

O


B O

O

B O

O


Si

Chemical Formula: C11H23BO2SiMolecular Weight: 226.1980

B O

O

S7

reaction mixture was allowed to stir at room temperature for 5 min. The reaction was quenched by exposing the reaction solution to air and adding CH2Cl2 (2 mL) to the solution. The crude reaction mixture was analyzed by GC-MS and then purified through a column chromatography (silica gel) using ethyl acetate/hexane (1:20, v/v) as an eluent. Colorless oil of 2l was isolated. Yield: 167 mg (86%). 1H NMR (500 MHz, CDCl3) δ 6.06 (dd, J = 17.8, 9.3 Hz, 1H), 5.49 (d, J = 17.8 Hz, 1H), 1.51 (dt, J = 8.8, 4.5 Hz, 1H), 0.86 – 0.73 (m, 2H), 1.25 (s, 12H), 0.53 (dd, J = 4.6, 2.1 Hz, 2H) ppm; 13C NMR (151 MHz, CDCl3) δ 158.6, 82.9, 24.8, 17.1, 7.9 ppm. GC-MS (m/z): 194 (calc. 194).

2m3: In a glovebox under N2 atmosphere, cobalt catalyst 1 (0.11 mg, 0.25 μmol, 0.025 mol%) and KOtBu (0.56 mg, 1 mol%) was dissolved in THF (1.0 mL) in a 3.8 mL glass vial equipped with a stir bar. The mixture was stirred for 1 min. 3-Hexyne (82 mg, 1.0 mmol) and pinacolborane (141 mg, 1.1 mmol) were then added. The reaction mixture was allowed to stir at room temperature for 10 min. The reaction was quenched by exposing the reaction solution to air

and adding CH2Cl2 (2 mL) to the solution. The crude reaction mixture was analyzed by GC-MS and then purified through a column chromatography (silica gel) using ethyl acetate/hexane (1:20, v/v) as an eluent. Colorless oil of 2m was isolated. Yield: 185 mg (88%). 1H NMR (500 MHz, CDCl3) δ 6.25 (t, J = 7.1 Hz, 1H), 2.12 (m, 4H, overlapping), 1.25 (s, 12H), 0.99 (t, J = 7.6 Hz, 3H), 0.93 (t, J = 7.6 Hz, 3H) ppm; 13C NMR (126 MHz, CDCl3) δ 147.1, 83.0, 24.8, 21.7, 21.6, 15.0, 13.9 ppm. GC-MS (m/z): 210 (calc. 210).

2n2: In a glovebox under N2 atmosphere, cobalt catalyst 1 (0.11 mg, 0.25 μmol, 0.025 mol%) and KOtBu (0.56 mg, 1 mol%) was dissolved in THF (1.0 mL) in a 3.8 mL glass vial equipped with a stir bar. The mixture was stirred for 1 min. 4-Octyne (110 mg, 1.0 mmol) and pinacolborane (141 mg, 1.1 mmol) were then added. The reaction mixture was allowed to stir at room temperature for 10 min. The reaction was quenched by exposing the reaction solution to air and adding CH2Cl2 (2 mL) to the solution. The crude reaction mixture was

analyzed by GC-MS and then purified through a column chromatography (silica gel) using ethyl acetate/hexane (1:20, v/v) as an eluent. Colorless oil of 2n was isolated. Yield: 155 mg (65%). 1H NMR (500 MHz, CDCl3) δ 6.28 (t, J = 7.1 Hz, 1H), 2.11 – 2.06 (m, 4H), 1.43 – 1.37 (m, 2H), 1.37 – 1.31 (m, 2H), 1.23 (s, 12H), 0.90 (t, J = 7.4 Hz, 3H), 0.86 (t, J = 7.3 Hz, 3H) ppm; 13C NMR (151 MHz, CDCl3) δ 146.3, 83.2, 30.96, 30.89, 25.0, 23.6, 22.7, 14.41, 14.37 ppm. GC-MS (m/z): 238 (calc. 238).

2o2: In a glovebox under N2 atmosphere, cobalt catalyst 1 (0.11 mg, 0.25 μmol, 0.025 mol%) and KOtBu (0.56 mg, 1 mol%) was dissolved in THF (1.0 mL) in a 3.8 mL glass vial equipped with a stir bar. The mixture was stirred for 1 min. Diphenylacetylene (178 mg, 1.0 mmol) and pinacolborane (141 mg, 1.1 mmol) were then added. The reaction mixture was allowed to stir at room temperature for 30 min. The reaction was quenched by exposing the reaction solution to air and adding CH2Cl2 (2 mL) to the solution. The crude reaction mixture was


B O

O


B O

O


B O

O

S8

analyzed by GC-MS and then purified through a column chromatography (silica gel) using ethyl acetate/hexane (1:20, v/v) as an eluent. White solid of 2o was isolated. Yield: 168 mg (55%). 1H NMR (500 MHz, CDCl3) δ 7.40 (s, 1H), 7.29 (d, J = 7.5 Hz, 2H), 7.25 (d, J = 7.0 Hz, 1H), 7.20 (d, J = 8.1 Hz, 2H), 7.17 – 7.12 (m, 3H), 7.11 – 7.06 (m, 2H), 1.34 (s, 12H) ppm; 13C NMR (126 MHz, CDCl3) δ 143.5, 130.3, 129.2, 128.6, 128.2, 127.9, 126.6, 84.1, 25.1 ppm. GC-MS (m/z): 306 (calc. 306).

2p + 2p'(1:1): In a glovebox under N2 atmosphere, cobalt catalyst 1 (0.11 mg, 0.25 μmol, 0.025 mol%) and KOtBu (0.56 mg, 1 mol%) was dissolved in THF (1.0 mL) in a 3.8 mL glass vial equipped with a stir bar. The mixture was stirred for 1 min. 4-Ethylphenyl-4-methoxyphenylacetylene (238 mg, 1.0 mmol) and

pinacolborane (141 mg, 1.1 mmol) were then added. The reaction mixture was allowed to stir at room temperature for 30 min. The reaction was quenched by exposing the reaction solution to air and adding CH2Cl2 (2 mL) to the solution. The crude reaction mixture was analyzed by GC-MS and then purified through a column chromatography (silica gel) using ethyl acetate/hexane (1:20, v/v) as an eluent. A mixture of 2p + 2p' as white solid was isolated. Yield: 306 mg (84%). 1H NMR (2p or 2p', 600 MHz, CDCl3) δ 7.28 (s, 2H), 7.12-7.08 (m, 2H, overlapping), 7.03-7.00 (m, 2H, overlapping), 6.96 (d, J = 8.3 Hz, 2H), 6.96 (d, J = 8.9 Hz, 2H), 3.74 (s, 3H), 2.65 (q, J = 7.6 Hz, 2H), 1.30 (s, 12H), 1.25 (t, J = 7.6 Hz, 3H) ppm; 13C NMR (126 MHz, CDCl3) δ 143.5, 130.3, 129.2, 128.6, 128.2, 127.9, 126.6, 84.1, 25.1 ppm. GC-MS (m/z): 364 (calc. 364). 1H NMR (2p', 600 MHz, CDCl3) δ 7.29 (s, 1H), 7.12-7.08 (m, 4H, overlapping), 7.03-7.00 (m, 2H, overlapping), 6.82 (d, J = 8.7 Hz, 2H), 3.81 (s, 3H), 2.56 (q, J = 7.6 Hz, 2H), 1.30 (s, 12H), 1.18 (t, J = 7.6 Hz, 3H) ppm. 13C NMR (2p + 2p', 151 MHz, CDCl3) δ 158.9, 158.0, 143.7, 142.8, 142.5, 141.9, 137.8, 134.5, 132.9, 131.5, 130.00, 129.96, 129.8, 128.7, 127.8, 127.4, 113.7, 113.2, 83.66, 83.61, 55.1, 28.6, 24.8, 15.4, 15.2 ppm. GC-MS (m/z): 364 (calc. 364).

2q + 2q' (2.5:1)2: In a glovebox under N2 atmosphere, cobalt catalyst 1 (0.11 mg, 0.25 μmol, 0.025 mol%) and KOtBu (0.56 mg, 1 mol%) was dissolved in THF (1.0 mL) in a 3.8 mL glass vial equipped with a stir bar. The mixture was stirred for 1 min. 1-Phenylpropyne (116 mg, 1.0 mmol) and pinacolborane (141 mg, 1.1 mmol) were then added. The reaction mixture

was allowed to stir at room temperature for 30 min. The reaction was quenched by exposing the reaction solution to air and adding CH2Cl2 (2 mL) to the solution. The crude reaction mixture was analyzed by GC-MS and then purified through a column chromatography (silica gel) using ethyl acetate/hexane (1:20, v/v) as an eluent. A mixture of 2q + 2q' as white solid was isolated. Yield: 127 mg (52%). 1H NMR (2q + 2q', 500 MHz, CDCl3) δ 7.44 – 7.32 (m, 4H), 7.30 – 7.21 (m, 2H), 7.21 – 7.17 (m, 2H), 6.79 – 6.73 (m, 1H), 2.03 (s, 1H, HC=CH-2q'), 1.80 (d, J = 7.0 Hz, 3H, HC=CH-2q), 1.35 (s, 5H, HBpin-2q'), 1.30 (s, 12H, HBpin-2q). 13C NMR (2q + 2q', 126 MHz, CDCl3) δ 143.1, 142.7, 140.1, 138.2, 129.7, 129.4, 128.4, 128.1, 127.4, 126.2, 83.84, 83.76, 25.18, 25.08, 16.34, 16.26 ppm. GC-MS (m/z): 244 (calc. 244).

B O

O

O +

B O

O

O

2p 2p'

B O

O

+

B OO

2q 2q'

S9

35: In a glovebox under N2 atmosphere, cobalt catalyst 1 (0.11 mg, 0.25 μmol, 0.025 mol%) and KOtBu (0.56 mg, 1 mol%) was dissolved in THF (1.0 mL) in a 3.8 mL glass vial equipped with a stir bar. The mixture was stirred for 1 min. 1-Hexyne (82 mg, 1.0 mmol) and pinacolborane (256 mg, 2.0 mmol) were then added. The reaction mixture was allowed to stir at room temperature for 10 min. The reaction was quenched by exposing the reaction solution to air and adding CH2Cl2 (2 mL) to the solution. The crude reaction mixture was analyzed by GC-MS and then purified through

a column chromatography (silica gel) using ethyl acetate/hexane (1:20, v/v) as an eluent. Colorless oil of 3 was isolated. Yield: 196 mg (58%). 1H NMR (500 MHz, CDCl3) δ 1.50 (q, J = 7.7 Hz, 2H), 1.28-1.21 (m, 6H), 1.20 (s, 12H), 1.19 (s, 12H), 0.82 (t, J = 6.9 Hz, 3H, HCH3), 0.68 (t, J = 7.9 Hz, 1H, HCH) ppm; 13C NMR (126 MHz, CDCl3) δ 83.1, 32.5, 32.1, 25.9, 25.1, 24.8, 22.8, 14.3 ppm. GC-MS (m/z): 338 (calc. 338).

Copies of NMR spectra for isolated products.

2a

BPin

1H NMR (600 MHz, CDCl3):

B O

O

Chemical Formula: C18H36B2O4Molecular Weight: 338.1020

BO O

S10

-2.0-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.012.5f1 (ppm)

12.0

1

1.00

1.03

2.10

1.09

2.01

1.32

1.32

6.16

6.19

7.26

7.29

7.30

7.33

7.34

7.35

7.39

7.42

7.48

7.50

7.50

13C NMR (151 MHz, CDCl3):

S11

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

25.1

5

83.6

9

127.

3912

8.89

129.

23

137.

78

149.

84

S12

2b

BPin


-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.5f1 (ppm)

23.9

3

1.00

2.03

1.05

2.00

1.35

1.35

6.15

6.18

7.39

7.41

7.41

7.44

7.46

7.48

S13

13C NMR (126 MHz, CDCl3):

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

25.1

3

31.5

5

35.0

0

83.5

7

125.

8112

7.13

135.

04

149.

7015

2.41

S14

2c

BPin

F


-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.012.5f1 (ppm)

12.2

3

0.98

2.07

1.00

1.98

1.31

1.31

6.05

6.09

7.00

7.01

7.02

7.02

7.04

7.33

7.37

7.44

7.45

7.46

7.46

7.47

S15

13C NMR spectrum (126 MHz, CDCl3):

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

24.8

2

83.4

2

115.

4911

5.66

128.

6912

8.75

148.

18

162.

1516

4.13

S16

2d

BPin

F

1H NMR spectrum (500 MHz, CDCl3):

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.5f1 (ppm)

12.1

9

1.00

1.36

1.16

1.38

2.08

1.31

6.22

6.26

7.02

7.03

7.05

7.10

7.11

7.13

7.55

7.57

7.58

7.60

S17


-100102030405060708090100110120130140150160170180190200210f1 (ppm)

24.9

0

29.8

0

83.5

4

115.

8111

5.99

124.

1612

4.19

125.

3712

5.46

127.

4312

7.46

130.

2413

0.30

141.

3714

1.40

159.

7616

1.77

S18

2e

BPin

Br


-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0f1 (ppm)

0

50

100

150

200

250

300

350

400

11.8

1

1.00

1.00

2.15

2.06

1.31

6.12

6.13

6.16

6.17

7.26

7.30

7.33

7.35

7.45

7.46

S19


-100102030405060708090100110120130140150160170180190200210f1 (ppm)

24.8

8

78.4

4

83.5

5

122.

97

128.

5813

1.66

131.

8113

3.61

136.

41

148.

14

S20

2f

BPin

O


-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.012.5f1 (ppm)

11.9

8

3.38

1.00

2.04

1.08

2.37

1.30

3.78

6.00

6.04

6.85

6.86

7.34

7.38

7.42

7.44

S21


-100102030405060708090100110120130140150160170180190200210f1 (ppm)

24.8

3

55.2

4

83.2

1

113.

9211

3.97

128.

48

133.

57

149.

10

160.

30

S22

2g

BPinO

O


-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

12.0

2

6.02

1.00

0.97

2.08

1.02

1.30

3.77

6.12

6.15

6.41

6.65

7.29

7.33

S23


-100102030405060708090100110120130140150160170180190200210f1 (ppm)

24.8

3

55.3

0

83.4

0

101.

29

104.

95

139.

48

149.

39

160.

81

S24

2h

BPin


-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

3.10

14.4

4

1.02

4.15

1.08

1.00

1.00

1.05

1.07

1.10

1.20

1.24

1.24

1.59

1.60

1.60

1.61

1.61

1.62

1.63

1.63

1.68

1.69

1.70

1.71

1.71

1.72

1.73

1.95

1.96

1.96

1.97

1.97

1.98

1.98

1.99

2.00

2.00

2.02

5.33

5.36

6.52

6.54

6.56

6.57

S25


-100102030405060708090100110120130140150160170180190200210f1 (ppm)

24.8

225

.99

26.2

0

31.9

4

43.2

9

82.9

8

159.

87

S26

2iBPin


-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.012.513.0f1 (ppm)

3.03

12.0

12.

052.

13

1.98

1.00

1.06

0.87

0.88

0.88

0.90

1.30

1.32

1.33

1.34

1.36

1.38

1.39

1.39

1.41

2.13

2.14

2.14

2.16

2.17

5.40

5.40

5.44

5.44

6.60

6.61

6.63

6.64

6.65

6.66

S27


-100102030405060708090100110120130140150160170180190200210f1 (ppm)

14.2

7

22.6

025

.11

30.6

8

35.8

6

83.3

2

155.

18

S28

2jBPin


-101234567891011121314f1 (ppm)

9.02

12.1

1

1.00

1.01

1.01

1.26

5.32

5.36

6.61

6.64

S29


-100102030405060708090100110120130140150160170180190200210f1 (ppm)

24.8

7

28.8

5

35.0

9

83.0

7

164.

49

S30

2kSi

BPin


-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

8.85

12.0

6

0.99

1.00

0.07

1.28

6.22

6.26

7.10

7.14

S31


-100102030405060708090100110120130140150160170180190200210f1 (ppm)

-1.7

7

24.8

9

83.4

5

158.

02

S32

2lBPin


-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.012.513.0f1 (ppm)

2.01

1.98

1.05

1.00

0.99

0.52

0.53

0.53

0.54

0.79

0.79

0.79

0.80

0.80

0.81

1.25

1.50

1.51

1.51

1.52

1.53

5.47

5.51

6.03

6.05

6.07

6.09

S33


-100102030405060708090100110120130140150160170180190200210f1 (ppm)

7.91

17.0

7

24.7

6

82.9

3

158.

64

S34

2m

Bpin


-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.012.5f1 (ppm)

3.11

3.11

12.1

8

4.07

1.00

0.91

0.91

0.92

0.93

0.93

0.93

0.94

0.95

0.97

0.97

0.98

0.99

0.99

0.99

1.00

1.01

1.25

2.10

2.11

2.11

2.12

2.13

2.14

2.15

6.24

6.25

6.26

S35


-100102030405060708090100110120130140150160170180190200210f1 (ppm)

13.9

014

.96

21.5

521

.74

24.8

1

83.0

2

147.

09

S36

2n

Bpin


-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.012.513.0f1 (ppm)

3.07

3.14

12.1

02.

242.

12

4.01

1.00

0.85

0.86

0.88

0.88

0.90

0.91

1.23

1.31

1.33

1.33

1.35

1.36

1.37

1.39

1.40

1.42

2.07

2.07

2.08

2.08

2.09

2.10

2.10

2.11

6.27

6.28

6.29

S37


-100102030405060708090100110120130140150160170180190200210f1 (ppm)

14.3

714

.41

22.7

223

.62

25.0

430

.89

30.9

6

83.2

0

146.

27

S38

2o

Bpin


-1.5-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.012.5f1 (ppm)

12.0

0

1.97

2.98

2.04

1.00

1.99

1.00

1.34

7.08

7.09

7.09

7.14

7.15

7.15

7.19

7.21

7.24

7.25

7.29

7.30

7.40

S39


-100102030405060708090100110120130140150160170180190200f1 (ppm)

25.1

2

84.1

1

126.

5812

7.90

128.

1612

8.56

129.

1613

0.27

137.

2614

0.71

143.

49

S40

B O

O

O +

B O

O

O

2p 2p'

1 : 1


0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)

3.10

3.20

22.8

5

2.00

2.09

2.94

3.05

1.94

2.01

1.97

3.84

5.75

2.03

1.16

1.18

1.19

1.24

1.25

1.26

1.27

1.30

1.30

1.31

1.32

2.54

2.55

2.56

2.58

2.63

2.64

2.65

2.66

3.74

3.81

6.64

6.66

6.81

6.83

6.95

6.97

7.00

7.01

7.01

7.02

7.02

7.08

7.09

7.10

7.10

7.11

7.11

7.12

7.28

7.29

S41


0102030405060708090100110120130140150160170f1 (ppm)

15.2

015

.36

24.8

0

28.5

7

55.1

2

83.6

183

.66

113.

2211

3.71

127.

3812

7.81

128.

7112

9.80

129.

9613

0.00

131.

4613

2.86

134.

5213

7.82

141.

8614

2.51

142.

7914

3.70

158.

0215

8.94

S42

B O

O

+

B OO

2q 2q'

2.5 : 1


-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

12.5

05.

24

3.00

1.21

1.00

2.05

2.49

4.27

1.30

1.35

1.79

1.81

2.03

6.73

6.75

6.75

6.76

6.76

6.78

7.18

7.18

7.19

7.20

7.23

7.24

7.25

7.25

7.27

7.27

7.29

7.29

7.29

7.33

7.34

7.35

7.35

7.36

7.36

7.37

7.37

7.38

7.39

7.39

7.41

7.43

S43


0102030405060708090100110120130140150160170f1 (ppm)

16.2

616

.34

25.0

825

.18

83.7

683

.84

126.

2012

7.42

128.

0812

8.36

129.

4112

9.74

140.

0614

2.68

143.

11

S44

3

Bpin

Bpin


-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)

1.00

3.00

0.80

23.5

27.

06

2.05

0.67

0.68

0.70

0.81

0.82

0.84

1.15

1.16

1.17

1.19

1.20

1.21

1.22

1.22

1.23

1.23

1.24

1.24

1.25

1.26

1.27

1.48

1.50

1.51

1.53

S45


-100102030405060708090100110120130140150160170180190200210f1 (ppm)

14.3

3

22.8

224

.80

25.1

425

.92

32.1

132

.52

83.1

3

S46

5

Bpin

D

H


0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)

GZ-1165-22-H.1.fid

12.1

6

0.01

1.10

2.08

1.00

2.16

1.34

1.35

6.21

7.30

7.31

7.33

7.35

7.36

7.38

7.43

7.44

7.44

7.52

7.53

7.53

*

2H NMR spectrum

-3-2-1012345678910111213141516f1 (ppm)

GZ-1165-22-2H.1.fid

6.23

6.26

S47


102030405060708090100110120130140150160170f1 (ppm)

GZ-1165-22-C.1.fid

24.9

1

83.4

1

127.

1412

8.65

128.

97

137.

55

149.

55

S48

References:

1. J. Wu, H. S. Zeng, J. Cheng, S. P. Zheng, J. A. Golen, D. R. Manke and G. Zhang, J. Org.

Chem. 2018, 83, 9442-9448.

2. M. Magre, B. Maity, A. Falconnet, L. Cavallo and M. Rueping, Angew Chem., Int. Ed., 2019,

58, 7025-7029.

3. A. Bismuto, S. P. Thomas and M. J. Cowley, Angew Chem., Int. Ed., 2016, 55, 15356-15359.

4. G. Zhang, J. Wu, H. Zeng, M. C. Neary, M. Devany, S. Zheng and P. A. Dub, ACS Catal.

2019, 9, 874-884.

5. Z. Zuo and Z. Huang, Org. Chem. Front. 2016, 3, 434-438.

New Internal Alkynes Catalysed by a Cobalt(II) Coordination Polymer … · 2019. 8. 1. ·...

Documents

Transcript of New Internal Alkynes Catalysed by a Cobalt(II) Coordination Polymer … · 2019. 8. 1. ·...